[go: up one dir, main page]

WO2025079368A1 - Initiateur de polymérisation cationique latent thermiquement, composition de résine durcissable et corps lié par un métal - Google Patents

Initiateur de polymérisation cationique latent thermiquement, composition de résine durcissable et corps lié par un métal Download PDF

Info

Publication number
WO2025079368A1
WO2025079368A1 PCT/JP2024/031612 JP2024031612W WO2025079368A1 WO 2025079368 A1 WO2025079368 A1 WO 2025079368A1 JP 2024031612 W JP2024031612 W JP 2024031612W WO 2025079368 A1 WO2025079368 A1 WO 2025079368A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymerization initiator
cationic polymerization
amine compound
lewis acid
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/031612
Other languages
English (en)
Japanese (ja)
Inventor
愛 松本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Publication of WO2025079368A1 publication Critical patent/WO2025079368A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/72—Complexes of boron halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a cationic polymerization initiator that is thermally latent and capable of controlling the initiation of polymerization of a compound having a cationic curable functional group by adjusting the temperature, a curable resin composition containing the cationic polymerization initiator, a bond between a cured product and a metal in which discoloration of the cured product and the metal under moist heat conditions is suppressed, use of a composition containing the cationic polymerization initiator and an amine compound as a thermally latent cationic polymerization initiator, a method for curing a curable resin composition containing the cationic polymerization initiator and a compound having a cationic curable functional group, a method for producing a cured product using the cationic polymerization initiator, and a cured product produced by the production method.
  • Epoxy resins are thermosetting and are widely used in electronic products such as printed circuit boards, memory, and CPUs due to their high electrical insulation, water resistance, and chemical resistance. In addition, due to their high corrosion resistance, they are also used as an ingredient in anti-corrosion paints for automobiles and ships. They are also used to paint the inside of beverage cans. They are also used as industrial adhesives, and in the construction industry as structural adhesives for concrete and steel plates. Recently, they have also been used as adhesives for lightweight, high-strength, high-performance materials such as carbon fiber and glass fiber.
  • Epoxy monomers are polymerized by cationic polymerization reactions. Compared to radical polymerization reactions, cationic polymerization reactions have the advantage that they are not inhibited by oxygen and shrinkage during curing is small. However, if polymerization begins immediately after mixing the epoxy monomer with the cationic polymerization initiator, there is a risk that the product will harden before it can be used.
  • the inventors' research group has therefore developed a thermally latent polymerization initiator composition that contains tris(pentafluorophenyl)borane, a cationic polymerization initiator, and a specific amine compound, and that does not initiate polymerization at room temperature but initiates polymerization at a lower temperature and has excellent catalytic ability (Patent Document 1). They have also developed a curable resin composition that contains a cationic curable compound having a cyclic ether group, a cationic curable compound having a double bond, and a specific boron compound, and that has excellent storage stability and can give a cured product with high transparency and uniformity with good productivity (Patent Document 2). They have also developed a polymerization initiator composition that contains a triaryl boron compound and a cyclic ether compound (Patent Document 3).
  • thermosetting epoxy resin compositions contain an epoxy resin, a specific aromatic amine compound, a specific boron-phosphorus complex, and a specific phosphorus compound, and can form a cured film with excellent voltage resistance, adhesion, and heat resistance in a short curing time (Patent Document 4).
  • Patent Document 5 discloses a curing catalyst that contains a Lewis acid and a monoamine or heterocyclic aromatic organic compound.
  • thermally latent resin compositions that begin to cure when heated are known.
  • the present inventors have found that some cured products of thermally latent resin compositions discolor the contact area with metal or the surrounding metal parts under moist and hot conditions. The discolored metal parts undergo deterioration of characteristics and corrosion, causing insulation failure.
  • an object of the present invention is to provide a cationic polymerization initiator that is thermally latent and capable of controlling the initiation of polymerization of a compound having a cationic curable functional group by adjusting the temperature, a curable resin composition containing the cationic polymerization initiator, a bond between a cured product and a metal in which discoloration of the cured product and the metal under moist and hot conditions is suppressed, use of a composition containing the cationic polymerization initiator and an amine compound as a thermally latent cationic polymerization initiator, a method for curing a curable resin composition containing the cationic polymerization initiator and a compound having a cationic curable functional group, a method for producing a cured product using the cationic polymerization initiator, and a cured product produced by the production method.
  • the present inventors have conducted extensive research to solve the above problems, and as a result, have found that in a composition containing a complex of a Lewis acid-type cationic polymerization initiator and an amine compound, the proportion of a free amine compound that does not form a complex is also important for the corrosion resistance of a cured product or metal, and have completed the present invention.
  • the present invention will now be described.
  • a method for producing an ink-jet printer comprising the steps of: the Lewis acid type cationic polymerization initiator and a part of the amine compound form a complex, the remainder of the amine compound is present free from the Lewis acid type cationic polymerization initiator, A thermally latent cationic polymerization initiator, characterized in that a molar ratio of amino groups contained in the free amine compound to 1 mole of boron atoms contained in the Lewis acid type cationic polymerization initiator is 0.15 or more and 1.70 or less.
  • F represents a fluoro group
  • R 1 represents a hydrocarbon group which may have a substituent
  • l represents an integer of 1 to 5
  • m represents an integer of 1 to 3
  • n represents an integer of 0 to 2
  • m+n 3
  • the two R 1s may be the same or different.
  • a printed wiring board comprising an insulating layer containing a cured product of the curable resin composition according to [6] above, and a conductor layer on one or both sides of the insulating layer.
  • a method for curing a curable resin composition comprising: Heating the curable resin composition, the curable resin composition contains a compound having a cationic curable functional group and a thermal latent cationic polymerization initiator, the thermal latent cationic polymerization initiator contains a Lewis acid type cationic polymerization initiator represented by formula (I) and an amine compound, the Lewis acid type cationic polymerization initiator and a part of the amine compound form a complex, the remainder of the amine compound is present free from the Lewis acid type cationic polymerization initiator,
  • the method according to claim 1 wherein the molar ratio of amino groups contained in the free amine compound to 1 mole of boron atoms contained in the Lewis acid type cationic polymerization initiator is 0.15 or more and 1.70 or less.
  • a method for producing a cured product comprising: A step of preparing a curable resin composition by mixing a compound having a cationic curable functional group and a thermal latent cationic polymerization initiator; Heating the curable resin composition, the thermal latent cationic polymerization initiator contains a Lewis acid type cationic polymerization initiator represented by formula (I) and an amine compound, the Lewis acid type cationic polymerization initiator and a part of the amine compound form a complex, the remainder of the amine compound is present free from the Lewis acid type cationic polymerization initiator,
  • the method according to claim 1 wherein the molar ratio of amino groups contained in the free amine compound to 1 mole of boron atoms contained in the Lewis acid type cationic polymerization initiator is 0.15 or more and 1.70 or less.
  • R 21 and R 22 are independently H, a C 1-6 alkyl group, a halogenated C 1-6 alkyl group, or a phenyl group, and R 21 and R 22 may together form a C 3-10 cycloalkyl group; and r represents an integer of 0 to 100.
  • the curable resin composition according to the present invention exhibits excellent thermal latency, probably because the Lewis acid type cationic polymerization initiator liberated by heating can catalyze the polymerization reaction of a compound having a cationic curable functional group. Therefore, the curable resin composition containing the thermally latent cationic polymerization initiator according to the present invention does not cure at room temperature, but begins to cure when heated, making it possible to control the curing by adjusting the temperature. Furthermore, the cured product of the curable resin composition according to the present invention is resistant to discoloration even under humid and hot conditions, and metals in contact with it are also resistant to discoloration, so it is useful, for example, as a component of the insulating layer of a metal-clad laminate in contact with metal. In addition, the cured product produced by the present invention is suppressed from defects such as coloring and cracking. Therefore, the present invention is extremely excellent in industry as a curable resin composition that not only can control curing, but also has excellent quality after curing.
  • FIG. 1 is a photograph showing the appearance of the cured products of Examples 1 and 2 and Comparative Examples 1 and 2.
  • the thermally latent cationic polymerization initiator according to the present invention contains a Lewis acid type cationic polymerization initiator represented by the above formula (I) (hereinafter referred to as "Lewis acid type cationic polymerization initiator (I)").
  • Thermal latent polymerization initiators are mainly divided into protonic acid type and Lewis acid type, but while protonic acid type produces a strong acid as a by-product by reacting with a compound having a cationic curing functional group, Lewis acid type does not produce a strong acid as a by-product, and the ligand coordinated to Lewis acid type cationic polymerization initiator functions as a stabilizer for the generated resin.
  • examples of the hydrocarbon group include aliphatic hydrocarbon groups selected from C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups.
  • examples of the C 1-6 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, and n-hexyl.
  • Preferred are C 1-4 alkyl groups, more preferred are C 1-2 alkyl groups, and even more preferred are methyl.
  • Examples of the C 2-6 alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, and hexenyl.
  • C 2-4 alkenyl groups more preferred are ethenyl (vinyl) and 2-propenyl (allyl).
  • Examples of C 2-6 alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, etc.
  • Examples of the substituent that the hydrocarbon group may have include one or more substituents selected from a C 1-6 alkoxy group, a halogeno group, a cyano group (--CN) and a nitro group (--NO 2 ).
  • the C1-6 alkoxy group refers to a linear or branched saturated aliphatic hydrocarbon oxy group having from 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy, etc., preferably a C1-4 alkoxy group, more preferably a C1-2 alkoxy group, and even more preferably methoxy.
  • halogeno groups include fluoro, chloro, bromo and iodo, with chloro or bromo being preferred and chloro being more preferred.
  • the number of substituents in the hydrocarbon group is not particularly limited as long as it is substitutable, but can be, for example, 1 or more and 8 or less.
  • the number is preferably 6 or less or 4 or less, more preferably 3 or less or 2 or less, and even more preferably 1.
  • the number l of fluoro groups on the phenyl group is preferably 2 or more or 3 or more, more preferably 4 or more, and even more preferably 5.
  • the number m of phenyl groups is preferably 2 or more, and more preferably 3.
  • Lewis acid type cationic polymerization initiator for example, tris(pentafluorophenyl)borane is preferred.
  • the amine compound according to the present invention refers to an organic compound having an amino group, but also includes ammonia (NH 3 ). That is, the amine compound according to the present invention is classified into ammonia, a primary amine compound, a secondary amine compound, and a tertiary amine compound.
  • the nitrogen atom of the amine compound is coordinated with the boron atom of the Lewis acid cationic initiator (I) to suppress the catalytic activity of the Lewis acid cationic initiator (I), but the catalytic activity of the Lewis acid cationic initiator (I) is expressed by dissociating both of them by heating. That is, the amine compound imparts thermal latency to the Lewis acid cationic initiator (I).
  • the primary amine compound is a compound (RNH 2 ) in which one of the hydrogen atoms of ammonia is substituted with a hydrocarbon residue.
  • Examples of the primary amine compound include the compound represented by the following formula (II 1 ). [Wherein, R2 represents a C1-6 alkyl group; p represents an integer of 0 to 5, q represents an integer of 1 to 6, p+q ⁇ 6; When p is an integer of 2 or more, two or more R 2s may be the same or different.
  • a secondary amine compound is a compound ( R2NH ) in which two hydrogen atoms of ammonia are replaced with a hydrocarbon residue, etc.
  • a tertiary amine compound is a compound ( NR3 ) in which three hydrogen atoms of ammonia are replaced with a hydrocarbon residue, etc.
  • Examples of secondary and tertiary amine compounds include compounds having a piperidine structure represented by the following formula ( II2 ). [Wherein, X represents an ether group (—O—) or a single bond; R 3 to R 7 independently represent H or a C 1-6 alkyl group.
  • Examples of the secondary amine compound and tertiary amine compound include compounds represented by the following formula (II 3 ) or (II 4 ). [Wherein, X and R 3 to R 7 are as defined above. Y represents a linker group or a single bond; R 8 represents H, a C 1-6 alkyl group, or the piperidine structure (II 2 ).
  • the linker group has the effect of increasing the positional freedom of the piperidine structure (II 2 ) and facilitating the synthesis of the compound, and is not particularly limited as long as it has such an effect.
  • the linked group can be, for example, a C 1-10 alkanediyl group having, at one or both ends, a group selected from the group consisting of an ether group, a thioether group, a carbonyl group, a thionyl group, an ester group, an amide group, a urea group, and a thiourea group.
  • R 9 to R 12 represent the piperidine structure (II 2 ) and the rest represent a C 1-20 alkyl group.
  • the amine compound is preferably a hindered amine compound.
  • a hindered amine compound is an amine compound in which the nucleophilicity of the lone electron pair of the nitrogen atom is weakened by steric hindrance due to a substituent.
  • an amine compound having a piperidine structure (II 2 ) in which R 4 to R 6 are all C 1-6 alkyl groups can be mentioned.
  • Examples of the hindered amine compound include the following compounds.
  • the amine compound may be an imidazole compound represented by the following formula: [In the formula, R 13 to R 16 independently represent a hydrogen atom (—H) or a C 1-6 alkyl group.] In the imidazole compound, R 16 is preferably a hydrogen atom.
  • a C1-6 alkyl group refers to a linear or branched monovalent saturated aliphatic hydrocarbon group having from 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, etc.
  • a C1-4 alkyl group is preferred, a C1-2 alkyl group is more preferred, and methyl is most preferred.
  • a single type of amine compound may be used, or a mixture of two or more types may be used.
  • the mixture may be a mixture of amine compounds differing only in the number of carbon atoms in the alkyl group, or a mixture of different types of amine compounds.
  • the number of amine compounds in the mixture is preferably 10 or less, more preferably 8 or less or 5 or less, and even more preferably 2.
  • An example of a mixture of amine compounds is a mixture of a hindered amine compound and an imidazole compound.
  • the ratio of the two types of amine compounds may be adjusted as appropriate depending on the thermal latent curing property, corrosion resistance, and the like.
  • the molar ratio of hindered amino groups to non-hindered amino groups may be 1 or more and 10 or less.
  • the molar ratio is preferably 2 or more or 3 or more, and is preferably 8 or less or 5 or less.
  • the thermally latent cationic polymerization initiator according to the present invention may contain a solvent. If it contains a solvent, it becomes easier to mix with a compound having a cationic curable functional group, and it becomes more convenient. On the other hand, from the viewpoint of storage stability, it does not have to contain a solvent.
  • the solvent is not particularly limited as long as it can adequately dissolve the Lewis acid type cationic polymerization initiator (I), the amine compound, and their complexes.
  • the solvent include alcohol solvents such as methanol, ethanol, and 2-propanol; ether solvents such as dimethyl ether, ethyl methyl ether, tetrahydrofuran, dioxane, and methoxycyclopentane; ketone solvents such as acetone and ethyl methyl ketone; ester solvents such as ethyl acetate and ⁇ -butyrolactone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene and toluene; halogenated hydrocarbon solvents such as dichloroethane, chloroform, carbon tetrachloride, and chlorobenzene;
  • the solvent preferably has a boiling point of 80°C or higher and 160°C or lower. If the boiling point is 80°C or higher, the curable resin composition can be sufficiently heated, and the curable resin composition can be sufficiently cured. If the boiling point is 160°C or lower, it is possible to prevent the curable resin composition from being excessively heated.
  • ether-based solvents having a boiling point of 80°C or higher and 160°C or lower are particularly preferred, and ether-based solvents having a boiling point of 90°C or higher and 120°C or lower are even more preferred. Furthermore, ether-based solvents having a boiling point of 90°C or higher and 110°C or lower are even more preferred, in that they can satisfactorily form a cured product such as a cured film that is free of cracks and has a uniform thickness.
  • the concentration may be adjusted as appropriate.
  • the total concentration of the Lewis acid type cationic polymerization initiator (I) and the amine compound may be adjusted to 10% by mass or more and 80% by mass or less, and preferably 25% by mass or more and 50% by mass or less.
  • Neutral three-coordinate boron compounds are called boranes and exhibit electron-accepting properties, and amine compounds have a lone pair of electrons on the nitrogen atom, so it is believed that the Lewis acid cationic polymerization initiator (I) and the amine compound form a complex.
  • the present inventors have found that even if the Lewis acid cationic polymerization initiator (I) and the amine compound are mixed so that the molar ratio of boron atoms to nitrogen atoms is 1:1, the two compounds do not necessarily form a complex with the exact amount, which is believed to depend mainly on the structure of the amine compound.
  • the inventors also discovered that by reacting a sufficient amount of an amine compound with the Lewis acid type cationic polymerization initiator (I) in a manner sufficient to form a complex with the Lewis acid type cationic polymerization initiator (I) and allowing a specific ratio of free amine compound to be present relative to the Lewis acid type cationic polymerization initiator (I), not only is thermal latency imparted to the Lewis acid type cationic polymerization initiator (I), but the inventors also discovered that a metal corrosion inhibitory effect is exhibited.
  • the free amine compound that is free from the Lewis acid type cationic polymerization initiator (I) may exist alone in the thermal latent cationic polymerization initiator, or may form a salt with, for example, another anion.
  • an amine compound is reacted with the Lewis acid cationic polymerization initiator (I) so that the amino group in the amine compound is more than 1 molar amount, thereby forming a complex between the Lewis acid cationic polymerization initiator (I) and the amine compound, and adjusting the molar ratio of the amino group contained in the free amine compound to 1 mole of boron atoms contained in the Lewis acid cationic polymerization initiator to 0.15 or more and 1.70 or less. If the molar ratio is 0.15 or more, the thermosetting property is more reliably exhibited.
  • the molar ratio is 1.70 or less, even if the cured product made with the thermal latent cationic polymerization initiator is in contact with metal, corrosion of the cured product itself and the metal can be suppressed.
  • the molar ratio is preferably 0.25 or more, more preferably 0.30 or more, and more preferably 1.50 or less, and more preferably 1.00 or less.
  • the "residual amine compound” refers to the amine compounds blended in the thermal latent cationic polymerization initiator other than the amine compounds that form a complex between the Lewis acid type cationic polymerization initiator and the amine compound.
  • the "residual amine compound” is present in the thermal latent cationic polymerization initiator as a free amine compound, independent of the thermal latent cationic polymerization initiator and the complex.
  • the amino group may refer to an -NH2 group, but in the present disclosure, the amino group is broadly defined to include not only an -NH2 group, but also an -NH- group in a secondary amine compound, an >N- group in a tertiary amine compound, and, when ammonia is used as the amine compound, ammonia itself.
  • the concentration and amount of the amine compound that exists free from the Lewis acid type cationic polymerization initiator can be measured by acid titration of the thermal latent cationic polymerization initiator.
  • the concentration and amount of the free amine compound shall be measured in accordance with the second method of 3. Amine value measurement method (2) of the Quasi-drug Raw Materials Standards 2006. Specifically, the thermal latent cationic polymerization initiator and bromophenol blue are dissolved in ethanol, and titrated with 0.5 mol/L hydrochloric acid until the solution turns green.
  • the amount of the free amine compound contained in the thermal latent cationic polymerization initiator can be calculated, and the molar ratio of the amino group contained in the free amine compound to 1 mole of boron atoms contained in the Lewis acid type cationic polymerization initiator can be calculated.
  • the thermally latent cationic polymerization initiator according to the present invention can be easily produced by simply mixing the Lewis acid cationic polymerization initiator (I) and the amine compound in a solvent.
  • the Lewis acid cationic polymerization initiator (I) and the amine compound may be mixed in a solvent at room temperature, more specifically, at 10°C or higher and 40°C or lower.
  • the solvent may be distilled off. Post-reaction treatment may be carried out according to a conventional method.
  • the curable resin composition according to the present invention contains the above-mentioned heat-latent cationic polymerization initiator and a compound having a cationic curable functional group.
  • the compound having a cationic curable functional group polymerizes by the cationic curable functional group attacking the cation generated from the heat-latent cationic polymerization initiator to generate a cation, which then attacks the cation generated by another cationic curable functional group.
  • Cationically curable functional groups include carbon-carbon double bond groups and cyclic ether groups. Examples include vinyl groups, epoxy groups, and oxetanyl groups.
  • Examples of the aliphatic unsaturated hydrocarbon include C 1-butene, 2-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3-methyl-1-pentene, 2,3-dimethyl-1-butene, 3,3-dimethyl-1-butene, vinylcyclopentane, 3,3-dimethyl-1-pentene, vinylcyclohexane, 1-octene, 2-octene, 2,4,4-trimethyl-1-pentene, vinylnorbornane, 1-decene, camphene, ⁇ -pinene, ⁇ -pinene, vinyladamantane, and the like.
  • 1-12 aliphatic unsaturated hydrocarbon compounds C 1-12 aliphatic unsaturated hydrocarbon compounds having two or more vinyl groups, such as butadiene, 1,4-pentadiene, cyclopentadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 2,5-norbornadiene, dicyclopentadiene, 4-vinyl-cyclohexene, 5-vinyl-2-norbornene, and 5-ethylidene-2- norbornene .
  • vinyl groups such as butadiene, 1,4-pentadiene, cyclopentadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 2,5-norbornadiene, dicyclopentadiene, 4-vinyl-cyclohexene, 5-vinyl-2-norbornene, and 5-ethylidene-2- norbornene .
  • aromatic compounds constituting the aromatic compound having a vinyl group include C6-18 aromatic compounds such as phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, etc.
  • aromatic compounds having a vinyl group include C6-18 aromatic compounds having one vinyl group such as styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-isopropylstyrene, 3-butylstyrene, 4-tert-butylstyrene, 4-hexylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, 2,4-diphenyl-4-methyl-1-pentene, 1-vinylnaphthalen
  • C6-18 aromatic compounds C6-18 aromatic compounds having two or more vinyl groups, such as 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,4-divinylnaphthalene, 1,5 -divinylnaphthalene, 1,4-diisopropenylnaphthalene, 9,10-divinylanthracene, allylstyrene, isopropenylstyrene, butenylstyrene, and octenylstyrene.
  • vinyl groups such as 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,4-divinylnaphthalene, 1,5 -divinylnaphthalene,
  • Cationically curable heteroatom-containing compounds are compounds that contain a cationic curable functional group containing a heteroatom, such as an epoxy group or an oxetanyl group, and polymerize by cations.
  • cationic curable heteroatom-containing compounds that have an epoxy group include epoxy resins with a cyclohexane skeleton, alicyclic epoxy resins, aliphatic epoxy resins, and aromatic epoxy compounds.
  • An example of an epoxy resin with a cyclohexane skeleton is the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.
  • alicyclic epoxy resins examples include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane, 1,2:8,9 diepoxy limonene, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, and hydrogenated epoxy compounds.
  • hydrogenated epoxy compounds include hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, hydrogenated bisphenol E type epoxy compounds, diglycidyl ethers of hydrogenated bisphenol A type alkylene oxide adducts, diglycidyl ethers of hydrogenated bisphenol F type alkylene oxide adducts, hydrogenated phenol novolac epoxy compounds, and hydrogenated cresol novolac epoxy compounds.
  • aliphatic epoxy resins include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, and polyethylene glycol diglycidyl ether.
  • aromatic epoxy compounds include aromatic bisphenol A type epoxy compounds, aromatic bisphenol F type epoxy compounds, aromatic bisphenol E type epoxy compounds, diglycidyl ethers of alkylene oxide adducts of aromatic bisphenol A type, diglycidyl ethers of alkylene oxide adducts of aromatic bisphenol F type, diglycidyl ethers of alkylene oxide adducts of aromatic bisphenol E type, aromatic novolac type epoxy compounds, urethane modified aromatic epoxy compounds, nitrogen-containing aromatic epoxy compounds, rubber modified aromatic epoxy resins containing polybutadiene or nitrile butadiene rubber (NBR), etc.
  • aromatic epoxy compounds include aromatic bisphenol A type epoxy compounds, aromatic bisphenol F type epoxy compounds, aromatic bisphenol E type epoxy compounds, diglycidyl ethers of alkylene oxide adducts of aromatic bisphenol A type, diglycidyl ethers of alkylene oxide adducts of aromatic bisphenol F type, diglycidyl ethers of alkylene oxide adducts
  • oxetane compounds which are cationic curable heteroatom-containing compounds having an oxetanyl group, include 3-ethyl-3-(alkoxymethyl)oxetanes such as 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(heptyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(octyloxymethyl)oxetane, and 3-ethyl-3-(dodecyloxymethyl)oxetane.
  • 3-ethyl-3-(alkoxymethyl)oxetanes such as 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(heptyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhex
  • the compound having a cationic curable functional group may be a bisphenol epoxy compound (III).
  • Some bisphenol epoxy compounds (III) are the main components of commercially available curable epoxy compound compositions, but curing with a cationic polymerization initiator requires high temperatures, and the cured product may crack or be discolored.
  • Curable epoxy compound composition products containing bisphenol epoxy compounds (III) include Acryset (registered trademark) BR series manufactured by Nippon Shokubai Co., Ltd. and jER TM series manufactured by Mitsubishi Chemical Corporation.
  • R 21 and R 22 are independently H, a C 1-6 alkyl group, a halogenated C 1-6 alkyl group, or a phenyl group, and R 21 and R 22 may together form a C 3-10 cycloalkyl group; and r represents an integer of 0 to 100.
  • r may be 0.
  • the upper limit of r is preferably 50 or less, more preferably 10 or less, and even more preferably 5 or less or 3 or less.
  • the ratio of the compound having a cationic curable functional group and the thermal latent cationic polymerization initiator in the curable resin composition according to the present invention may be adjusted as appropriate within a range in which the compound having a cationic curable functional group can be cured well.
  • the mass ratio of the compound having a cationic curable functional group to 1 part by mass of the Lewis acid type cationic polymerization initiator (I) contained in the latent cationic polymerization initiator may be adjusted to about 50 or more and 200 or less.
  • the ratio is preferably 60 or more, more preferably 80 or more, and is preferably 150 or less, more preferably 120 or less.
  • Additives such as antistatic agents, curing agents, flame retardants, antibacterial agents, antioxidants, and pigments may also be blended into the curable resin composition of the present invention. It is also suitable to blend particles such as silica particles to improve the linear expansion coefficient and electrical properties.
  • rubber particles can also improve the impact resistance of the cured product.
  • examples of rubber particles include acrylic rubber particles, silicone rubber particles, and fluororubber particles.
  • particle size of the rubber particles but for example, those with a volume-based average particle size of 0.05 ⁇ m or more and 2 ⁇ m or less can be used.
  • amount of rubber particles incorporated in the curable resin composition but it can be, for example, 10 phr or more and 30 phr or less.
  • a compound having a cationic curable functional group and a thermal latent cationic polymerization initiator are mixed to prepare a curable resin composition.
  • the thermal latent cationic polymerization initiator according to the present invention contains a Lewis acid type cationic polymerization initiator (I) and an amine compound.
  • the curable resin composition prepared in the step 1 is molded.
  • the molding method is not particularly limited and may be appropriately selected, and examples thereof include spin coating, solvent casting, dipping, spray coating, and dispenser methods.
  • the spin coating method is a method of coating a flat substrate with a liquid using centrifugal force, and this method can form a liquid curable resin composition into a thin film.
  • the solvent casting method is a method of pouring a liquid curable resin composition into a mold to form a mold.
  • the dipping method is a method of immersing a mold or a substrate that serves as a core in a liquid curable resin composition to form a coating of the liquid curable resin composition on the substrate surface.
  • the spray coating method is a method of spraying a liquid curable resin composition onto a substrate surface to form a coating of the liquid curable resin composition on the substrate surface.
  • the dispenser method is a method of discharging a fixed amount of liquid curable resin composition onto a substrate from a device called a dispenser to form a coating of the liquid curable resin composition on the substrate surface.
  • Curing step In this step, the curable resin composition is cured by heating.
  • the curable resin composition according to the present invention does not cure at room temperature due to the action of the thermal latent cationic polymerization initiator according to the present invention, which is a polymerization catalyst. However, by heating, the thermal latent cationic polymerization initiator according to the present invention exerts its polymerization catalytic ability, and the composition cures.
  • the curing initiation temperature for the thermal latent cationic polymerization initiator of the present invention is preferably 50°C or higher. This is because if the curing initiation temperature is 50°C or higher, curing is unlikely to start at room temperature.
  • the temperature is more preferably 60°C or higher or 80°C or higher, and even more preferably 100°C or higher.
  • the heating temperature is preferably 500°C or lower, more preferably 400°C or lower, even more preferably 300°C or lower, and even more preferably 200°C or lower.
  • the thermally latent cationic polymerization initiator according to the present invention is believed to dissociate from the amine compound when heated, initiating the polymerization reaction. It is unclear whether the amine compound dissociated from the thermally latent cationic polymerization initiator forms a complex with the thermally latent cationic polymerization initiator again after the polymerization reaction, or whether it remains free. However, for example, amine compounds with low boiling points, such as ammonia, may evaporate from the cured product and their concentration may fall below the detection limit.
  • the bonded body according to the present invention contains a cured product of the curable resin composition and a metal, and the cured product and the metal are in contact with each other. As described above, the bonded body according to the present invention has excellent corrosion resistance between the cured product and the metal.
  • the metal contained in the bonding body is not particularly limited, but examples include copper, gold, silver, nickel, aluminum, and alloys of stainless steel, with copper, silver, and nickel being preferred from the standpoints of electrical conductivity, ease of handling, cost, etc.
  • the shape of the metal is not particularly limited and may be appropriately selected, and may be, for example, spherical, plate-like, tubular, bulk, linear, sponge-like, etc.
  • the plate-like shape may be a foil having a thickness of about 5 ⁇ m or more and 200 ⁇ m or less. The thickness is preferably 10 ⁇ m or more, and more preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 20 ⁇ m or less.
  • the shape of the cured product is not particularly limited, and can be, for example, spherical, plate-like, tubular, bulk, linear, or sponge-like.
  • the thickness of the plate-like product can be selected appropriately, and can be, for example, 10 ⁇ m or more and 500 ⁇ m or less.
  • the thickness is preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 50 ⁇ m.
  • a sheet formed from fibers such as carbon fibers can be impregnated with a curable resin composition containing a solvent to form a prepreg.
  • a prepreg can be laminated with metal foil and heated to cure the curable resin composition to form a metal-clad laminate.
  • the curable resin composition of the present invention can also be used as an adhesive between metals or between metals and other components, a conductive paste containing conductive metals, an anisotropic conductive film (ACF) material, a sealant for circuit elements with exposed metal parts, etc.
  • ACF anisotropic conductive film
  • the combination of Lewis acid type cationic polymerization initiator (I) and amine compound can polymerize and harden epoxy monomers well at relatively low temperatures.
  • bisphenol epoxy resin (III) cannot be polymerized unless it is at high temperatures with conventional thermal latent cationic polymerization initiators, and even if it can be polymerized, defects such as discoloration and cracks may occur.
  • the combination of Lewis acid type cationic polymerization initiator (I) and amine compound according to the present invention makes it possible to polymerize and harden bisphenol epoxy resin (III) at relatively low temperatures while suppressing defects.
  • the cured product produced by the method of the present invention can also be used as a protective layer for printed wiring boards.
  • the curable resin composition of the present invention is layered on a flexible, insulating plastic film such as polyester or polyimide so as to cover the conductor pattern of a flexible printed wiring board in which the conductor pattern is formed by printing technology, and the curable resin composition is cured by applying heat and pressure, thereby obtaining a flexible printed wiring board provided with a protective layer.
  • the cured or semi-cured product of the present invention may be used as a resin film or prepreg.
  • the curable resin composition of the present invention may be applied to a release film, and then cured or semi-cured by heating, and formed into a film to form a resin film or prepreg.
  • Semi-curing is, for example, B-staging.
  • R represents an unspecified hydrogen atom or an organic group, and multiple Rs may be the same or different.
  • bisphenol epoxy resin (III) has two epoxy groups, its cured product may have a three-dimensional or higher-order structure. As a result, while analysis of the chemical structure of a polymer is generally difficult, analysis of the chemical structure of a cured product of bisphenol epoxy resin (III) is even more difficult.
  • the present invention allows the epoxy monomer to be polymerized at a relatively low temperature, it is believed that at least a portion of the Lewis acid type cationic polymerization initiator (I) remains in the cured product.
  • some amine compounds have a low boiling point, such as ammonia, the content of the amine compound in the cured product may be below the detection limit.
  • Catalyst Production Example 1 Production of cationic polymerization initiator 1-1 To tris(pentafluorophenyl)borane (0.906 g, 1.770 mmol, hereinafter abbreviated as “TPB”) was added 2 mol/L ammonia-2-propanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., containing 0.695 g, 1.770 mmol ammonia), and the mixture was stirred for 1 hour until dissolved.
  • TPB tris(pentafluorophenyl)borane
  • Catalyst Production Example 2 Production of cationic polymerization initiator 1-2 To TPB (0.906 g, 1.770 mmol) was added 2 mol/L ammonia-2-propanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., containing 0.834 g, 2.124 mmol ammonia), and the mixture was stirred for 1 hour until dissolved.
  • Catalyst Production Example 3 Production of cationic polymerization initiator 1-3 To TPB (0.906 g, 1.770 mmol) was added 2 mol/L ammonia-2-propanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., containing 0.903 g, 2.301 mmol ammonia), and the mixture was stirred for 1 hour until dissolved.
  • Catalyst Production Example 4 Production of cationic polymerization initiator 1-4 To TPB (0.906 g, 1.770 mmol) was added 2 mol/L ammonia-2-propanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., containing 1.042 g, 2.655 mmol ammonia), and the mixture was stirred for 1 hour until dissolved.
  • Catalyst Production Example 5 Production of cationic polymerization initiator 1-5 To TPB (0.906 g, 1.770 mmol) was added 2 mol/L ammonia-2-propanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., containing 1.390 g, 3.540 mmol ammonia), and the mixture was stirred for 1 hour until dissolved.
  • Catalyst Production Example 6 Production of cationic polymerization initiator 1-6 To TPB (0.906 g, 1.770 mmol) was added 2 mol/L ammonia-2-propanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., containing 2.084 g, 5.309 mmol ammonia), and the mixture was stirred for 1 hour until dissolved.
  • Catalyst Production Example 7 Production of cationic polymerization initiator 2-1 To TPB (10.556 g, 20.617 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid ("ADEKA STAB LA57", manufactured by ADEKA Corporation, 2.039 g, 2.577 mmol) and methoxycyclopentane (14.000 g) were added, and the mixture was stirred for 1 hour until dissolved.
  • ADEKA STAB LA57 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid
  • methoxycyclopentane (14.000 g
  • Catalyst Production Example 8 Production of cationic polymerization initiator 2-2 To TPB (10.556 g, 20.617 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid having the following chemical structure ("ADEKA STAB LA57", manufactured by ADEKA Corporation, 2.854 g, 3.608 mmol) and methoxycyclopentane (14.000 g) were added, and the mixture was stirred for 1 hour until dissolved.
  • ADEKA STAB LA57 manufactured by ADEKA Corporation, 2.854 g, 3.608 mmol
  • methoxycyclopentane (14.000 g
  • Catalyst Production Example 9 Production of cationic polymerization initiator 2-3 To TPB (10.556 g, 20.617 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid ("ADEKA STAB LA57", manufactured by ADEKA Corporation, 3.262 g, 4.123 mmol) and methoxycyclopentane (14.000 g) were added, and the mixture was stirred for 1 hour until dissolved.
  • ADEKA STAB LA57 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid
  • methoxycyclopentane (14.000 g
  • Catalyst Production Example 10 Production of cationic polymerization initiator 2-4 To TPB (10.556 g, 20.617 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid ("ADEKA STAB LA57", manufactured by ADEKA Corporation, 4.077 g, 5.154 mmol) and methoxycyclopentane (14.000 g) were added, and the mixture was stirred for 1 hour until dissolved.
  • ADEKA STAB LA57 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid
  • methoxycyclopentane (14.000 g
  • Catalyst Production Example 11 Production of cationic polymerization initiator 2-5 To TPB (10.556 g, 20.617 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid ("ADEKA STAB LA57", manufactured by ADEKA Corporation, 4.485 g, 5.669 mmol) and methoxycyclopentane (14.000 g) were added, and the mixture was stirred for 1 hour until dissolved.
  • ADEKA STAB LA57 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid
  • methoxycyclopentane (14.000 g
  • Catalyst Production Example 12 Production of cationic polymerization initiator 2-6 To TPB (10.556 g, 20.617 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid ("ADEKA STAB LA57", manufactured by ADEKA Corporation, 5.300 g, 6.700 mmol) and methoxycyclopentane (14.000 g) were added, and the mixture was stirred for 1 hour until dissolved.
  • ADEKA STAB LA57 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid
  • methoxycyclopentane (14.000 g
  • Catalyst Production Example 13 Production of cationic polymerization initiator 2-7 To TPB (10.556 g, 20.617 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid (manufactured by Adeka Corporation, "ADEKA STAB LA57", manufactured by Adeka Corporation, 8.154 g, 10.308 mmol) and methoxycyclopentane (14.000 g) were added, and the mixture was stirred for 1 hour until dissolved.
  • TPB 1,2,3,4-butanetetracarboxylic acid
  • Catalyst Production Example 14 Production of cationic polymerization initiator 3-1 A hindered amine-based light stabilizer having the following chemical structure ("TINUVIN765" manufactured by BASF, 6.309 g, 12.370 mmol) and methoxycyclopentane (14.000 g) were added to TPB (10.556 g, 20.617 mmol) and stirred for 1 hour until dissolved.
  • TINUVIN765 manufactured by BASF, 6.309 g, 12.370 mmol
  • methoxycyclopentane (14.000 g) were added to TPB (10.556 g, 20.617 mmol) and stirred for 1 hour until dissolved.
  • Test Example 1 Measurement of free amine value The free amine value of the produced cationic polymerization initiator was measured. Bromophenol blue was dissolved in ethanol to prepare a 0.1% by mass ethanol solution, hereinafter referred to as BPB solution. A cationic polymerization initiator (1 g) and a BPB solution (0.2 mL) were added to a vial containing ethanol (10 mL), and the vial was then capped and stirred for about 5 seconds. 0.5 mol/L hydrochloric acid (Kishida Chemical Co., Ltd.) was gradually added dropwise to the resulting solution. The solution color was confirmed to change from blue to green to yellow, and the point where the solution turned green was determined as the end point.
  • BPB solution 0.1% by mass ethanol solution
  • the amine compound that formed a complex with TPB did not react with hydrochloric acid, and the number of moles of hydrochloric acid required for dropping corresponded to the number of moles of amino groups contained in the free amine.
  • the number of moles of amino groups contained in free amines per mole of boron in the cationic polymerization initiator subjected to measurement is taken as the free amine value, and is shown together with the molar ratio (N/B) of the amine compound to boron in the TPB used in the production of the cationic polymerization initiator in Tables 1 and 2.
  • the commercially available cationic polymerization initiator used for comparison (“SAN-AID SI-80L” manufactured by Sanshin Chemical Industry Co., Ltd.) does not contain free amines in its structure. However, when the initiator was similarly measured just to be sure, the color of the solution was yellow from the beginning, and therefore the free amine value was determined to be 0.
  • Resin composition production example 1 A resin composition was obtained by uniformly mixing 1 part by mass of a cationic polymerization initiator with 100 parts by mass of an alicyclic epoxy compound ("Celloxide 2021P" manufactured by Daicel Corporation) for 5 minutes. For comparison, a resin composition was obtained in the same manner using a commercially available cationic polymerization initiator having the following chemical structure ("San-Aid SI-80L” manufactured by Sanshin Chemical Industry Co., Ltd.). Some of the resin compositions were cured at this point.
  • Test Example 2 Thermosetting test The resin composition, which was uncured at the time of mixing, was dropped onto a copper plate of 0.3 ⁇ 50 ⁇ 50 mm and spin-coated at 1000 rpm for 10 seconds. The copper plate coated with the resin composition was heated on a hot plate heated to 120° C. for 1 hour to be thermoset.
  • Test Example 3 Highly Accelerated Life Test Using a highly accelerated life tester ("PC-242HS-E” manufactured by Hiranuma Seisakusho Co., Ltd.), each copper plate on which the resin composition was thermally cured was held under harsh conditions of 100% RH and 120°C for 96 hours, after which the appearance was observed and evaluated according to the following criteria. The results are shown in Table 3.
  • a resin composition containing the cationic polymerization initiator according to the present invention which has a free amine value relative to boron of 0.15 or more and 1.70 or less, exhibits thermosetting properties, that is, it does not cure at room temperature but cures upon heating, and the appearance of the cured product formed thereby does not change even when it comes into contact with metal under moist and hot conditions. Therefore, the cationic polymerization initiator composition and resin composition according to the present invention are very useful for forming a cured resin that can be cured in a controlled manner and that comes into contact with a metal, such as an insulating layer for a circuit board.
  • Catalyst Production Example 15 Production of cationic polymerization initiator 4-1 A hindered amine-based light stabilizer having the following chemical structure ("TINUVIN770" manufactured by BASF, 4.956 g, 10.309 mmol) and methoxycyclopentane (14.000 g) were added to TPB (10.556 g, 20.617 mmol) and stirred for 1 hour until dissolved.
  • TINUVIN770 manufactured by BASF
  • Catalyst Production Example 16 Production of cationic polymerization initiator 5-1 To TPB (10.556 g, 20.617 mmol), 2-ethyl-4-methylimidazole having the following chemical structure (manufactured by Tokyo Chemical Industry Co., Ltd., 0.408 g, 3.711 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid (manufactured by Adeka Corporation, "ADEKA STAB LA57", Adeka Corporation, 2.935 g, 3.711 mmol), and methoxycyclopentane (14.000 g) were added and stirred for 1 hour until dissolved.
  • 2-ethyl-4-methylimidazole having the following chemical structure (manufactured by Tokyo Chemical Industry Co., Ltd., 0.408 g, 3.711 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracar
  • Catalyst Production Example 17 Production of cationic polymerization initiator 5-2 To TPB (10.556 g, 20.617 mmol), 2-ethyl-4-methylimidazole (Tokyo Chemical Industry Co., Ltd., 0.863 g, 7.832 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid (ADEKA CORPORATION, "ADEKA STAB LA57”, ADEKA CORPORATION, 2.935 g, 3.711 mmol), and methoxycyclopentane (14.000 g) were added and stirred for 1 hour until dissolved.
  • TPB 10.556 g, 20.617 mmol
  • 2-ethyl-4-methylimidazole Tokyo Chemical Industry Co., Ltd., 0.863 g, 7.832 mmol
  • Catalyst Production Example 18 Production of cationic polymerization initiator 5-3 To TPB (10.556 g, 20.617 mmol), 2-ethyl-4-methylimidazole (Tokyo Chemical Industry Co., Ltd., 1.544 g, 14.019 mmol), 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid (ADEKA CORPORATION, "ADEKA STAB LA57”, ADEKA CORPORATION, 2.935 g, 3.711 mmol), and methoxycyclopentane (14.000 g) were added and stirred for 1 hour until dissolved.
  • TPB 10.556 g, 20.617 mmol
  • 2-ethyl-4-methylimidazole Tokyo Chemical Industry Co., Ltd., 1.544 g, 14.019 mmol
  • 2,2,6,6-tetramethyl-4-piperidine ester of 1,2,3,4-butanetetracarboxylic acid (
  • Resin composition production example 2 A resin composition was obtained in the same manner as in Resin Composition Production Example 1, except that 100 parts by mass of an aromatic epoxy compound ("YL980" manufactured by ADEKA CORPORATION) was used instead of the alicyclic epoxy compound ("Celloxide 2021P” manufactured by Daicel Corporation).
  • the thermosetting property of each resin composition was tested in the same manner as in Test Example 2, and the highly accelerated life of the cured product of each resin composition and the copper plate in contact with the cured product was tested in the same manner as in Test Example 3. The results are shown in Table 4.
  • the resin composition containing the cationic polymerization initiator according to the present invention which contains not only a hindered amine as an amine compound but also an imidazole compound in addition to the hindered amine and has a free amine value relative to boron of 0.15 to 1.70, and an aromatic epoxy compound, does not cure at room temperature but cures upon heating, and the appearance of the cured product formed thereby does not change even when in contact with metal under moist and hot conditions, and the appearance of the metal in contact with the cured product does not change either.
  • the cationic polymerization initiator composition and resin composition according to the present invention are very useful for forming a cured resin that can be cured in a controlled manner and that comes into contact with a metal, such as an insulating layer for a circuit board.
  • Resin composition production example 3 An alicyclic epoxy compound or aromatic epoxy compound shown in Table 5 and a cationic polymerization initiator were mixed in the mass ratio shown in Table 6 to obtain a resin composition.
  • Test Example 5 Differential Scanning Calorimetry Using a differential scanning calorimeter ("DSC 3500" manufactured by Netzsch Japan Co., Ltd.), the heat generation characteristics of the curable resin composition were measured. The measurement conditions were a temperature rise rate of 10°C/min, and the measurement was performed from 30°C to 250°C in a nitrogen atmosphere. The results are shown in Table 8.
  • Test Example 6 Dynamic Viscoelasticity Measurement A dynamic viscoelasticity measuring device ("DMA RSA-G2" manufactured by TA Instruments Japan) was used to measure the storage modulus, loss modulus and tan ⁇ of the cured product. The measurement conditions were three-point bending, a temperature rise rate of 5°C/min, measurement from 30°C to 250°C, a normal load of 10 g and a sensitivity of 2 g. The sample size was 5 mm x 20 mm x thickness 2 mm. The results are shown in Table 9.
  • DMA RSA-G2 Dynamic Viscoelasticity measuring device manufactured by TA Instruments Japan
  • Dynamic elastic modulus includes storage elastic modulus (Pa) and loss elastic modulus (Pa), storage elastic modulus is the component of energy generated by external force and strain that is stored inside the object, and loss elastic modulus is the component that diffuses to the outside. Tan ⁇ is called the loss factor and is expressed as loss elastic modulus / storage elastic modulus, and the larger the value, the higher the viscosity and the easier it is to diffuse energy generated by strain to the outside, so it can be said to be more resistant to impact.
  • the cured products of Examples 3 to 5 according to the present invention have a high Tg of 100°C or higher and a high tan ⁇ compared to the cured product of Comparative Example 3 using a commercially available initiator. Therefore, it can be said that the cured products can diffuse external strain and have high impact resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)

Abstract

Le but de la présente invention est de fournir : un initiateur de polymérisation cationique qui est latent thermiquement et qui est capable de commander l'initiation de la polymérisation d'un composé qui a un groupe fonctionnel durcissable par voie cationique par réglage de la température ; une composition de résine durcissable qui contient l'initiateur de polymérisation cationique ; un corps lié d'un produit durci et d'un métal, la décoloration du produit durci et du métal dans des conditions de chaleur humide étant supprimée ; l'utilisation d'une composition qui contient l'initiateur de polymérisation cationique et un composé amine en tant qu'initiateur de polymérisation cationique latent thermiquement ; un procédé de durcissement d'une composition de résine durcissable qui contient l'initiateur de polymérisation cationique et un composé qui a un groupe fonctionnel durcissable par voie cationique ; un procédé de production d'un produit durci à l'aide de l'initiateur de polymérisation cationique ; et un produit durci qui est obtenu par le procédé de production. Un initiateur de polymérisation cationique latent thermiquement selon la présente invention est caractérisé en ce qu'il contient un initiateur de polymérisation cationique de type acide de Lewis spécifique et un composé amine, l'initiateur de polymérisation cationique de type acide de Lewis et une partie du composé amine formant un complexe ; le reste du composé amine étant libéré de l'initiateur de polymérisation cationique de type acide de Lewis ; et le rapport molaire des groupes amino contenus dans le composé amine libre sur 1 mole d'atomes de bore contenus dans l'initiateur de polymérisation cationique de type acide de Lewis étant de 0,15 à 1,70 inclus.
PCT/JP2024/031612 2023-10-10 2024-09-03 Initiateur de polymérisation cationique latent thermiquement, composition de résine durcissable et corps lié par un métal Pending WO2025079368A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2023-175040 2023-10-10
JP2023175040 2023-10-10
JP2024-034825 2024-03-07
JP2024034825 2024-03-07

Publications (1)

Publication Number Publication Date
WO2025079368A1 true WO2025079368A1 (fr) 2025-04-17

Family

ID=95395697

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/031612 Pending WO2025079368A1 (fr) 2023-10-10 2024-09-03 Initiateur de polymérisation cationique latent thermiquement, composition de résine durcissable et corps lié par un métal

Country Status (2)

Country Link
JP (1) JP2025066056A (fr)
WO (1) WO2025079368A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012036164A1 (fr) * 2010-09-15 2012-03-22 株式会社日本触媒 Composition utilisable comme initiateur de polymérisation à chaleur latente
JP2016017147A (ja) * 2014-07-09 2016-02-01 株式会社日本触媒 樹脂組成物及びその用途
JP2019116556A (ja) * 2017-12-27 2019-07-18 京セラ株式会社 エポキシ樹脂組成物およびリフレクター
JP2021165355A (ja) * 2020-04-08 2021-10-14 株式会社日本触媒 熱潜在性重合開始剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012036164A1 (fr) * 2010-09-15 2012-03-22 株式会社日本触媒 Composition utilisable comme initiateur de polymérisation à chaleur latente
JP2016017147A (ja) * 2014-07-09 2016-02-01 株式会社日本触媒 樹脂組成物及びその用途
JP2019116556A (ja) * 2017-12-27 2019-07-18 京セラ株式会社 エポキシ樹脂組成物およびリフレクター
JP2021165355A (ja) * 2020-04-08 2021-10-14 株式会社日本触媒 熱潜在性重合開始剤

Also Published As

Publication number Publication date
JP2025066056A (ja) 2025-04-22

Similar Documents

Publication Publication Date Title
TWI440648B (zh) 用於固化環氧化物之觸媒
TWI424006B (zh) 熱硬化性聚醯亞胺矽樹脂組成物及其硬化皮膜
KR20140043762A (ko) 경화성 조성물
TW200923006A (en) Liquid epoxy resin forming formulation containing inorganic particles
JP5688146B2 (ja) コポリマー
TWI439486B (zh) 用於固化環氧化物之觸媒
US20250122404A1 (en) Polymer, composition, cured product, laminated body, and electronic component
TW201638175A (zh) 組成物、環氧樹脂固化劑、環氧樹脂組成物、熱固化性組成物、固化物、半導體裝置以及層間絕緣材料
JP2025061379A (ja) エポキシ樹脂組成物、エポキシ樹脂硬化物
JP5527600B2 (ja) エポキシ樹脂組成物及びそれを用いた電子部品装置
WO2025079368A1 (fr) Initiateur de polymérisation cationique latent thermiquement, composition de résine durcissable et corps lié par un métal
WO2015052907A1 (fr) Composition d'un dérivé de benzofuranne, composition d'un précurseur de polyimide, et procédé de production d'une résine de polyimide
JPS62288670A (ja) エポキシ樹脂系粉体塗料組成物
Kaya et al. Synthesis, characterization and some properties of epoxy resins containing azomethine bonding
JP7038565B2 (ja) 熱硬化性エポキシ樹脂組成物、接着剤、エポキシ樹脂硬化物、塩、及び硬化剤
TW200911866A (en) Catalyst for curing epoxides
TW201636356A (zh) 鏻化合物、含有其的環氧樹脂組成物及使用其製造的半導體裝置
TW202536039A (zh) 熱致性陽離子聚合起始劑、固化性樹脂組合物及金屬接合體
JPS61209222A (ja) ジカルボニルキレ−ト
JP4509539B2 (ja) エポキシ樹脂組成物シート
KR20150011747A (ko) 포스포늄 이온 함유 화합물, 이를 포함하는 에폭시수지 조성물, 및 이를 사용하여 제조된 장치
US9890238B2 (en) Curing catalyst for epoxy resin composition, epoxy resin composition comprising same, and apparatus manufactured by using same
JPH0586422B2 (fr)
TW202012536A (zh) 環氧樹脂組成物、印刷配線基板以及半導體密封材料
JPH0586420B2 (fr)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24876967

Country of ref document: EP

Kind code of ref document: A1